Storage structure for a solid electrolyte battery

ABSTRACT

A storage medium and an inert material, either integrated into the storage medium or existing as a separate phase in the storage medium, form a storage structure. The inert material at least partially contains or is formed by a polymorphous inert material. The polymorphous inert material has at least one polymorphous phase transition in the range between ambient temperature and maximum operating temperature of the solid electrolyte battery. The polymorphous phase transition induces a distortion of the lattice structure of the inert material, thus causing a change in the specific volume and acting on the surrounding grains of the storage medium. A mechanical coupling of the stresses triggered by the phase transition of the inert material causes the neighboring grains of the storage medium to break apart, such that new reactive zones become available in the storage medium, thereby regenerating the solid electrolyte battery.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is the U.S. national stage of International ApplicationNo. PCT/EP2014/060041, filed, May 16, 2014 and claims the benefitthereof. The International Application claims the benefit of GermanApplication No. 102013210342.5 filed on Jun. 4, 2013, both applicationsare incorporated by reference herein in their entirety.

BACKGROUND

Described below is a storage structure for a solid electrolyte battery.

Solid electrolyte batteries are based on the operating principle ofsolid electrolyte fuel cells, which are extended by additional provisionof at least one storage element to give a solid electrolyte battery.

Known solid electrolyte fuel cells of the generic type, for exampleoxide-ceramic fuel cells, also referred to in the specialist field asSOFC (solid oxide fuel cells), are known from international publishedspecification WO 2011/019455 A1, in which the concept of SOFC-derivedsolid electrolyte batteries is addressed in detail. Solid electrolytebatteries of this kind work with an operating temperature above 500° C.,at which the solid electrolyte has sufficient ion conductivity foroxygen ions.

A storage medium intended for operation of a rechargeable solidelectrolyte battery typically includes particles suitable for formationof a redox pair as a constituent of at least one storage element of thesolid electrolyte battery. The particles are typically formed of metaland/or metal oxide. According to the battery state (charging ordischarging), this storage medium is reduced or oxidized. The storagestructure typically has a gas-permeable porous microstructure, i.e. askeleton-like structure of the storage medium with high open porosity.

In a multitude of cyclical charging and discharging operations, i.e.reduction and oxidation operations, of the storage medium, the storagemedium at the high operating temperatures applied has a tendency tocoarsening and/or sintering of the particles of the active storagemedium. This leads to a continuous change in the storage structure andespecially to a decrease in the surface area of the storage medium,which is reflected in increasingly poorer charging and dischargingcharacteristics and in a decrease in the useful capacity.

There have therefore already been proposals of storage structures usingstorage media based on oxide dispersion-strengthened particles (ODS)particles. Such a storage structure features more prolonged stability,which corresponds to a higher achievable number of cycles of chargingand discharging operations without any significant losses in usefulcapacity. Additionally known is use of a ceramic matrix which forms anintergranular (i.e. between the particles of the storage medium) supportskeleton to space apart the particles of the storage medium.

Both dispersion strengthening of the particles of the storage medium anda coarse-grained ceramic matrix slow down coarsening of the particles ofthe storage medium, but cannot reverse it. More particularly, it is notpossible at present to regenerate an aged storage structure to theeffect that particle coarsening of the storage medium is reversed.

SUMMARY

The storage structure includes a storage medium and an inert materialintegrated in the storage medium or present as a separate phase in thestorage medium, wherein the inert material contains or is formed atleast in part by a portion of a polymorphous inert material. Thepolymorphous inert material has at least one polymorphous phasetransition within the range between room temperature and the maximum usetemperature of the solid electrolyte battery.

The polymorphous phase transition brings about a change in the latticestructure and the specific volume of the inert material, which alsoaffects the surrounding grains of the storage medium by acting on them.Mechanical coupling of the change in volume triggered by the phasetransition of the inert material leads to tensions in the environment ofthe inert material and thus causes the adjacent grains of the storagemedium to break up, thus providing new reactive zones of the storagemedium. Thus, regeneration of the solid electrolyte battery is achieved.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other aspects and advantages will become more apparent andmore readily appreciated from the following description of the exemplaryembodiments, taken in conjunction with the accompanying drawings ofwhich:

FIG. 1 is a schematic diagram of an illustrative setup and a mode ofoperation of a solid electrolyte battery;

FIG. 2 is a schematic diagram of a storage structure of the solidelectrolyte battery; and

FIG. 3 is a phase diagram of an illustrative polymorphous inertmaterial.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Reference will now be made in detail to the preferred embodiments,examples of which are illustrated in the accompanying drawings, whereinlike reference numerals refer to like elements throughout.

The figures, for the benefit of an informative representation, are notnecessarily drawn true to scale; more particularly, the size ratios ofthe figure elements shown—both in themselves and relation to oneanother—do not necessarily correspond to reality.

FIG. 1 shows an illustrative structure diagram for representation of amode of operation of a solid electrolyte battery, to the extentnecessary for the description of the present invention. Because of theschematic representation, therefore, not all components of such a solidelectrolyte battery are illustrated.

A mode of operation of a solid electrolyte battery includes supplying aprocess gas, especially air, via a gas supply 14 at a positiveelectrode—arranged at the bottom in the drawing and symbolized by acircled plus sign—which is also referred to as air electrode 16, andremoval of oxygen from the air in the course of discharge—according to acircuit shown on the right-hand side of the picture. The oxygen passesin the form of oxygen ions O²⁻ through a solid electrolyte 18 adjoiningthe positive electrode to a negative electrode 20—arranged at the top inthe drawing and symbolized by a circled minus sign—which is alsoreferred to as a storage electrode. The latter is connected via agaseous redox pair, for example a hydrogen-water vapor mixture, to aporous storage structure 2.

If an impervious layer of the active storage medium were to be presentat the negative electrode 20, the charge capacity of the solidelectrolyte battery would be rapidly exhausted. For this reason, it isappropriate to use a storage structure 2 composed of porous material andcontaining a functional oxidizable material as storage medium, such asmetal or metal oxide, for example iron and iron oxide and/or nickel andnickel oxide, as storage medium at the negative electrode 20.

A redox pair which is gaseous in the operating state of the battery, forexample a mixture of H₂/H₂O, transports oxygen ions through thesolid-state electrolyte 18, after they have been discharged at thenegative electrode, in the form of water vapor through pore channels inthe porous storage structure 2 of the active storage medium. Accordingto whether a discharging or charging operation is in progress, the metalor metal oxide is oxidized or reduced and the oxygen required for thepurpose is provided by the gaseous redox pair H₂/H₂O or transported backto the solid-state electrolyte 18 or to the negative electrode 20. Thismechanism of oxygen transport via a gaseous redox pair is also referredto as the shuttle mechanism.

The diffusion of the oxygen ions through the solid electrolyte 18requires a high operating temperature of 600 to 900° C. in the solidelectrolyte battery described. The operating temperature range isadditionally advantageous for an optimal composition of the gaseousredox pair H₂/H₂O in equilibrium with the storage medium. At such anoperating temperature, not only are the electrodes 16 and 20 and theelectrolyte 18 subjected to high thermal stress, but also the storagestructure 2 of the storage medium. In the constant cycles of oxidationand reduction, the active storage medium has a tendency to sinter and/orto coarsen.

Sintering means that individual grains increasingly fuse to one anotheras a result of diffusion processes, with a disadvantageous decrease bothin the reactive surface area and in the completely open pore structurewhich is required for the gas transport.

Coarsening means that individual grains grow at the expense of othergrains, with a disadvantageous decrease in the numerical density andreactive surfaces of the grains.

In a closed pore structure, the redox pair H₂/H₂O is no longer able toreach the active surface area of the active storage medium, and so,after only a partial discharge of the storage medium, the internalresistance of the battery becomes very high, which prevents any furthertechnically viable discharge.

FIG. 2 shows a significantly enlarged representation of a microstructureof the storage structure used in a solid electrolyte battery.

The storage structure is formed essentially by the redox-active storagemedium SM and inert material IN. The storage medium SM is in principlepresent in any desired grain form. The schematic representation of thedrawing shows, by way of example, large oval grain cross sections.

Pores are present between the grains of the storage medium SM.

By virtue of the open porosity formed, shuttle gas, especially H₂/H₂O,is able to flow in the desired manner through the storage structure. Acharging or discharging process brings about a reduction or oxidation ofthe grains of the active storage medium SM, the oxidation state of whichincreases during the oxidation and decreases again in the course ofreduction. Oxidation and reduction processes are associated with aconstant change in volume of the grains of the active storage medium SM.

To prevent mutual sintering and/or coarsening of the grains of theactive storage medium SM, an inert material IN is introduced into thestorage structure, the inert material IN being in any desired form, forexample in the form of grains of any size or else in the form ofwhisker-shaped particles (not shown).

The particles of the inert material IN are arranged both in anintragranular and in an intergranular manner in relation to the grainsof the storage medium, and therefore within and/or between the grains ofthe storage medium SM. In this manner, the particles of the inertmaterial IN, even after several oxidation and reduction cycles, canspace apart the individual grains of the storage medium SM from oneanother, since no spread of the active storage medium SM through theinert material IN takes place even after several charging/dischargingcycles. Nor does any chemical reaction take place between the inertmaterial IN and the shuttle gas H₂/H₂O.

If the inert material IN is distributed in an intragranular manner inthe storage material, what are called ODS (oxidedispersion-strengthened) particles of the storage material may beformed. For production of these ODS particles, iron particles are usedand are mixed with coarse-grain zirconium dioxide ZrO₂, pressed dry andlightly sintered. Both the ceramic particles of inert material INpresent in intragranular form in the storage material and acoarse-grained ceramic matrix of inert material IN (not shown) slow downcoarsening of the storage medium SM. The ceramic-based inert materialused to form the ceramic matrix at present is, for example,yttrium-stabilized zirconium dioxide, also referred to as YSZ, e.g., ina composition referred to as 8YSZ, having a concentration of 8 mol % ofY₂O₃ is ZrO₂.

Continued redox cycling in the solid electrolyte battery then leads, incombination with the high operating temperatures, to gradual coarseningof the active storage medium and hence to noticeable aging in thebattery performance.

A further problem lies in the intrinsic oxidation mechanism of thestorage metals used, which is based principally on cationic diffusion.This oxidation mechanism leads, especially in the discharging operation,to gradual migration of the storage medium in the direction of the O²⁻source, since the diffusion of the metal species into the reaction zoneis faster than the corresponding transport of the oxygen species in theunderlying oxidation process.

The resulting mass flow toward the oxidation source leads, together withthe gradual coarsening and/or sintering of the reactive metal particlesoriginally present, to a continuous change in the storage structure,which is reflected in increasingly poorer charging and dischargingcharacteristics and in a decrease in the useful capacity.

The described use of inert material IN in the composition of the storagestructure is able to slow down coarsening of the storage medium SM, butis unable to reverse it. More particularly, it is not possible atpresent to regenerate an aged storage structure.

Typical aging-related particle coarsening of the active storage mediumis reversed by aiming to increase the active surface areas of thestorage medium SM again or else to deagglomerate them. Thisdeagglomeration assures regeneration of an aged storage structure.

For regeneration of the storage structure, use of a polymorphous inertmaterial IN is employed, the inert material IN having at least onepolymorphous phase transition within a temperature range that can bechosen to a substantial degree via technical measures. The temperaturerange may be within a range between room temperature and a maximum usetemperature of the solid electrolyte battery.

The term “polymorphous” is understood to mean the property of a compoundof being able to exist in several lattice structures each havingdifferent chemical and/or physical properties. Polymorphous materialsthus differ by the three-dimensional arrangement of their latticestructures and thus have different properties. Different latticestructures can be established as a result of various outside influences,and in this context it is the influence of temperature which is ofcrucial interest. The phase transition is, in this context, a change inthe lattice structure of the inert material IN because of a temperaturechange.

The polymorphous phase transition, via the change in lattice structure,also brings about a greater or lesser change in the specific volume ofthe inert material IN, which acts on the surrounding grains of thestorage medium SM in the form of a mechanical tension. Mechanicalcoupling of the stresses triggered by the phase transition of the inertmaterial IN causes the adjacent grains of the storage medium SM to breakup, providing new reactive zones of the storage medium for the redoxoperation. Accordingly, a regenerative deagglomeration is achieved.

A polymorphous phase transition is established, for example, by virtueof a thermal cycle of the storage structure passing through the phasetransition temperature. The mechanical stresses caused by the changedlattice structure and the associated change in volume of the inertmaterial IN cause the storage structure to break up, providing newreactive zones for the redox operation in the charging or dischargingprocess.

A temperature range for performance of the regeneration process is inprinciple in a range between room temperature and a maximum usetemperature of the solid electrolyte battery. The process can thus beused either in a special regeneration operation outside a thermaloperating range for normal storage operation or else within the thermaloperating range of normal storage operation, which is also referred toas the intrinsic operating temperature band.

According to a configuration, the polymorphous phase transitiontemperature is within the intrinsic operating temperature band. Duringthe discharging operation, the storage medium SM is oxidized, which istypically an exothermic operation and leads to heating of the solidelectrolyte battery. By contrast, the reduction of the active storagemedium SM is generally an endothermic process and leads to cooling ofthe solid electrolyte battery. The temperature window covered istypically 700-850° C., which thus constitutes the range for thepolymorphous phase transition temperature of the inert matrix materialIN.

According to an alternative configuration, lower transition temperaturesdown to room temperature are selected for the polymorphous phasetransition temperature of the inert material IN. The surface area of theactive storage medium SM is then increased by regenerative operationemploying a controlled cooling and reheating operation of the solidelectrolyte battery.

An example of an inert polymorphous matrix material used is zirconiumdioxide, which is suitably doped with an element from the group of therare earths (RE), for example according to the structural formulaZrO₂-(RE)O_(1.5). Rare earth dopants, represented by “RE” as aplaceholder in the structural formula, may be yttrium, neodymium,lanthanum, cerium and/or gadolinium, and combinations thereof.

For further elucidation of the material properties utilized, FIG. 3shows a phase diagram of an illustrative polymorphous inert material,using doping based on neodymium according to the structural formulaZrO₂-NdO_(1.5) to illustrate the phase transitions. Plotted on theabscissa of the phase diagram is the molar proportion MFR of NdO_(1.5)in relation to the pure undoped matrix material ZrO₂, which rises from0% on the left-hand side of the phase diagram to 100% on the right-handside of the abscissa of the phase diagram. Plotted on the ordinate ofthe phase diagram is the temperature TMP, with the temperatures TMPplotted rising from the bottom upward.

Drawn on the phase diagram is a dotted line between a first coordinate 1and a second coordinate 2 which runs parallel to the ordinate and hencecorresponds to a temperature rising between the first coordinate 1 andthe second coordinate 2 at a given molar proportion MFR of NdO_(1.5) inrelation to the undoped matrix material ZrO₂. As can be seen in thephase diagram, the doped material runs here between the lowertemperature TMP of the first coordinate 1 and the higher temperature TMPof the second coordinate 2 of a polymorphous phase transition, namelyfrom a monoclinic phase M to a tetragonal phase T. In the reversedirection, corresponding to a lowering of the temperature TMP, the dopedmaterial undergoes a phase transition from a tetragonal phase T to amonoclinic phase.

The other phases F, P, L, A, X and H named in the drawing are notessential to the understanding of this phase transition underconsideration, and are merely cited for the sake of completeness.

The phase transition from the monoclinic phase M to the tetragonal phaseT has a displacing martensitic effect on the lattice structure of thedoped inert material, leads to a considerable change in volume of theunit cell of several percent and is therefore particularly suitable forbringing about the mechanical stresses. When the doping in question isused in an inert material IN, these stresses cause the adjacent grainsof the storage medium to break up, providing new reactive zones for theredox operation in the charging or discharging process.

The choice of a temperature range for performance of the regenerationprocess should be made on the basis of a thermal level of phasetransitions as a function of a selected doping. The temperature range isin principle within a range between room temperature and a maximum usetemperature of the solid electrolyte battery. Considerations have to bemade for setting of the temperature for special regenerative operationabove the intrinsic operating temperature band. An upper operatingtemperature limit for current solid electrolyte batteries nowadays istypically about 900° C. It is possible to operate the solid electrolytebattery temporarily in a temperature range exceeding the upper operatingtemperature limit up to the maximum use temperature of the solidelectrolyte battery, in order to conduct temporary regenerativeoperation of the solid electrolyte battery, in which case thetemporarily increased temperature range of the regenerative operationexceeds the nowadays customary upper operating temperature limit. In theindividual case, a consideration has to be made as to whether theadvantages of an elevated temperature range above the upper operatingtemperature limit which is to be established for regenerative operationoutweigh the disadvantages of growth in thermal aging processes abovethe upper operating temperature limit. The maximum use temperature ofthe solid electrolyte battery, in the context of the aforesaid, is aparameter of a solid electrolyte battery which is not fixed in principleand arises solely from the technical consideration in the above sense.

What may be more technically viable is regenerative operation selectedoutside the thermal cycle of normal storage operation in a lowertemperature range down to room temperature. In each case, if thetemperature range for performance of the regeneration process is withinthe intrinsic operating temperature band of the solid electrolytebattery, the regeneration will take place within the normal temperatureband of charging and discharging operation.

Through the choice of an inert material IN suitable in terms of thethermal level of its phase transitions, it is technically possible toestablish a suitable temperature range on the basis of the inertmaterial selected and on the basis of suitable doping. The choice ofZrO₂-NdO_(1.5) as inert material IN has been found to be technicallyfavorable, but is merely illustrative of a polymorphous inert materialIN and has at least one polymorphous phase transition in the rangebetween room temperature and the maximum use temperature of the solidelectrolyte battery.

The polymorphous inert material IN may either be integrated in theactive storage medium SM or may be present as a separate phase in thestorage structure.

The total content of polymorphous inert material is advantageously lessthan 50 percent by volume.

According to one embodiment, the rare earth content, i.e. the molarproportion MFR of (RE)O_(1.5) in relation to the undoped inert materialZrO₂, is less than 10%, or even less than 5%, since, in this case, thetetragonal-monoclinic phase transition of the ZrO₂ associated with arelative large change in volume is within the abovementionedadvantageous operating temperature range.

The storage structure allows the creation of new reactive surfaces ofthe active storage medium. This results in a distinct reduction in theaging rate and a distinct improvement in the long-term stability of thestorage medium.

The storage structure additionally allows upscalable, reproducible,flexible and inexpensive production of the storage medium and isapplicable to various metal storage materials.

A description has been provided with particular reference to preferredembodiments thereof and examples, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the claims which may include the phrase “at least one of A, B and C”as an alternative expression that means one or more of A, B and C may beused, contrary to the holding in Superguide v. DIRECTV, 358 F3d 870, 69USPQ2d 1865 (Fed. Cir. 2004).

1-8. (canceled)
 9. A storage structure for a solid electrolyte battery, comprising a storage medium and inert material, comprising: at least a portion of polymorphous inert material which, within a range between room temperature and a maximum use temperature of the solid electrolyte battery, has at least one polymorphous phase transition.
 10. The storage structure as claimed in claim 9, wherein at least one polymorphous phase transition temperature of the polymorphous inert material is within an intrinsic operating temperature band of the solid electrolyte battery.
 11. The storage structure as claimed in claim 9, wherein the polymorphous inert material used is rare earth-doped zirconium dioxide.
 12. The storage structure as claimed in claim 11, wherein a molar rare earth content of the rare earth-doped zirconium dioxide is less than 10 percent.
 13. The storage structure as claimed in claim 12, wherein the molar rare earth content of the rare earth-doped zirconium dioxide is less than 5 percent.
 14. The storage structure as claimed in claim 11, wherein the rare earth dopants of the rare earth-doped zirconium dioxide is at least one material selected from the group consisting of yttrium, neodymium, lanthanum, cerium and gadolinium.
 15. The storage structure as claimed claim 9, wherein a total proportion of the polymorphous inert material in the storage structure is below 50 percent by volume.
 16. The storage structure as claimed in claim 9, wherein the polymorphous inert material is integrated within the storage medium.
 17. The storage structure as claimed in claim 9, wherein the polymorphous inert material is a separate phase in the storage medium.
 18. The storage structure as claimed in claim 9, wherein the storage medium is at least one material selected from the group consisting of iron, iron oxide, nickel, nickel oxide, tungsten and tungsten oxide. 